1-amino-4-[aroylaminomethyl-alkylsubstituted-amino]-anthraquinone-2-sulfonic acids



United States Patent 3 320 287 1 AMINO 4 ARoYLAMINoMETHYL ALKYL- SUBSTHTUTED AMINO] ANTHRAQUIN ONE 2- SULFONIC ACIDS Hans Rudolf Schwander, Riehen, near Basel, Switzerland,

assignor to J. R. Geigy A.G., Basel, Switzerland N0 Drawing. Filed June 8, 1965, Ser. No. 462,410

Claims priority, applicatgonlgvsvitzerland, July 24, 1959,

3 3 Claims. (Cl. 260372) This is a continuation-in-part of our pending application Serial No. 44,528, filed July 22, 1960 and now abandoned.

The present invention concerns new anthraquinone dyestuffs, processes for the production thereof and their use for the dyeing and printing of fibers containing polypeptide groups. The invention also concerns the industrial products produced by the use of these new dyestuflis.

It has been found that valuable new anthraquinone dyestuffs are obtained of the formula wherein A represents an m-valent radical of an anthraquinone dyestud,

B represents a divalent aromatic radical bound to the anthraquinone nucleus by a hetero atom from the group of N, O and S atoms,

X represents the acyl radical of an aromatic monocarboxylic acid, and

m and n represent low whole numbers,

if an anthraquinone compound, which contains at least one aromatic radical bound to the anthraquinone nucleus by way of a hetero atom from the group of N, O and S atoms and which has at least one replaceable hydrogen atom at the anthraquinone nucleus, is treated with the N-methylol compound of an aromatic 'monocarboxylic acid amide or with a functional derivative thereof which reacts like this methylol compound until at least one XNHCH radical is introduced and the reaction product, if necessary, is sulphonated.

The new anthraquinone dyestuffs can also contain more aroylamidomethyl groups as defined. This is the case, for example, on using starting products in which the anthraquinone nucleus is substituted by further condensable aromatic radicals. However, more of such aroylamidomethyl groups can be bound to a single substituent if the latter is only mononuclear; they can also be bound to a single nucleus. The number of such groups which are characteristic of the new dyestufls which are introduced into the anthraquinone compound on reaction with the methylol compound depends in the first place on the nature of the aromatic radicals bound at the anthraquinone nucleus. However, in many cases by the choice of suitable reaction conditions, the number of aroylamidornethyl groups to be introduced can also be influenced or even determined. It is thus often possible to introduce the number of such groups which is most favourable for the properties of the end products. Anthraquinone compounds according to the invention having one aroylamidomethyl group per aromatic radical are particularly valuable dyestuffs.

The new anthraquinone dyestuffs according to the general formula I contain at least one sulphonic acid group. This water solubilising :substituent is already present advantageously in the anthraquinone compound used as reaction component. However, this group or other such groups can often be introduced in a simple manner either during or after the condensation reaction by sulphonation. In general, the presence of more than three sulphonic acid groups in the end product is not desirable. I The anthraquinone compounds used in the present process as starting products which contain at least one aromatic radical bound to the anthraquinone nucleus by a nitrogen, oxygen or sulphur atom should be of the series of the simple anthraquinonyl compounds. As such are utilised in particular the anthraquinonyl-ot,oU-diamino, aaminoanthraquinonyl-a-imino, a,m'-diaminoanthraquinonyl-B-oxy and a,a-diaminoanthraquinonyl-B,{5"-dioxy compounds. Particularly easily accessible and therefore preferred starting products used according to the invention are, for example, 1-amino-2-sulphoanthraquinonyl-4- a-minoaryl-, l-aminoor l-alkylaminoanthraquinonyl-4- aminoaryl, anthraquinonyl-l,4- or -l,5-diaminoaryl, 1,4- diaminoanthraquinonyl-2-oxyaryl or -2-thioaryl or -2,3 dioxyaryl or -2,3-dithioaryl and l-amino-4-arylaminoanthraquinonyl-Z-oxyaryl compounds. The anthraquinone nuclei themselves can also be still further substituted, for example, by halogen, particularly by chlorine or bromine, and also by methyl, hydroxyl and sulphonic acid groups.

Advantageously the aromatic radicals bound to the anthraquinone nuclei by N, O or S atoms are of the isocyclic series. Particularly, they are radicals of the benzene series, thus, for example, phenyl, diphenyl, styryl, diphenylether, diphenylthioether, diphenylamine, benzoylaminophenyl and benzylphenyl radicals. The aromatic radicals can contain the substituents usual in anthraquinone dyestuffs, thus, chiefly alkyl groups such as, e.g. methyl, ethyl, propyl, butyl and amyl groups; or cycloalkyl groups such as, e.g. the cyclohexyl group; then halogens such as chlorine, bromine and fluorine; also alkoxy groups such as, e.g. methoxy, ethoxy and butoxy groups;

then also nitro, acid amide, acid ester, sulphonic acid, alkylsulphonyl, alkylamino and acylamino groups. The condition is that the arylamino or aryloxy or arylthio groups in the aryl radical contain at least one replaceable hydrogen atom in order to be able to react with the other reaction component, i.e. with the N-methylol compound of the aryl carboxylic acid amide. The more nucleophilic the aryl radical is under the reaction conditions, the easier.

is the condensation with the methylol compound. Good yields and uniform condensation products are thus obtained principally with those anthraquinone compounds which contain only nucleophilically substituted arylamino or aryloxy or arylthio groups.

' From the aforesaid it can be seen that in the anthraquinone compounds used as starting products, the aryl substituents should, if possible, be of the benzene series; in addition they should be bound advantageously by way of an imino group at an a-position of the anthraquinone nucleus and should be substituted, advantageously, only by nucleophilic groups.

The aroyl-N-methylolamldes used as second reaction component in the process according to the invention are obtained by adding formaldehyde to the corresponding aromatic monocarboxylic acid amides in the presence of basic condensing agents such as, e.g. potassium carbonate, or in the presence of mineral acid also, in this case under mild conditions. A'dvantageoilsly the known and easily accessible primary amides of monoor polynuclear mono-carboxylic acids, e.g. those of the benzene, naphthalene, diphenyl, diphenylether, diphenyla-mine and diphenylketone monocarboxylic acids are used as aromatic monocarboxylic acid amides. Also mixtures of carboxylic acid amides can be used, for example, the amides of mixtures of aromatic monocarboxylic acids obtained by oxidising a mixture of benzene homologues or a mixture of halogenated toluenes or also those obtained by chlorinating benzoyl chloride. However, in the present process chiefly the N-methylol compounds of benzene monocarboxylic acid amides are used. The benzene nuclei can contain the substituents usual in anthraquinone dyestufls, in particular those mentioned above. N-methylolbenzamide and its halogenated, in particular chlorinated, derivatives are the preferred reaction components both in view of their easier accessibility and also in view of the good dyeing properties of the end products obtained therefrom.

The anthraquinone compounds are condensed with the methylol compounds in the presence of acid condensing agents or of agents which split off water and react like acid condensing agents. As such, principally concentrated hydrochloric acid, zinc chloride, phosphorus pentoxide, acetic acid anhydride, viscous phosphoric acid and oleum are used. However, the preferred condensing agent is concentrated anhydrous sulphuric acid as generally it can serve simultaneously as solvent for the reaction components. The reaction temperature can vary between wide limits and depends chiefly on the condensing agent used. In concentrated sulphuric acid the reaction generally proceeds quickly and completely at room temperature. In some cases, a raised temperature is necessary, for example 4080, particularly when a number of aryolamidomethyl groups are to be introduced. This, however, is under the proviso that the reaction components are not decomposed under these conditions and that a possible sulphonation of the reaction product is not undesirable. The final reaction products are precipitated by pouring the sulphuric acid solutions or suspensions into ice water and then isolating in the usual way.

Instead of the aryl carboxylic acid-N-methylolamides, also reactive functional derivatives of these methylol compounds can be used provided they react in the same way. For example, the esters obtained by treating the methylol compounds with inorganic or organic acids or acid halides or anhydrides, or also the di-(aroylamidomethyl)-ethers obtained by self-condensation in the presence of, e.g. phosphorus oxychloride can be used. However, as these functional derivatives have generally to be produced from the corresponding methylol compounds, the first process is altogether preferred. It is possible, though, in single cases in which unsatisfactory results are obtained with the methylol compounds, to attain the goal with these derivatives, particularly with the N-chloromethylamides. In some cases, the process according to the invention can be simplified with good results by reacting in one vessel a mixture of the dyestuif with formaldehyde or a polymer thereof and with the aroylamide instead of starting with the completely formed methylol compounds of the amides.

A modified process for the production of dyestuffs according to the invention consists in forming the anthraquinone compounds from components of which at least one already contains at least one aryolamidomethyl group of the formula X--NH-CH This is done by reacting an anthraquinone compound and an aromatic compound each of which contains a reactive substituent, in which reaction the components are condensed. The aromatic compound used in this reaction is one which already contains at least one aroylamidomethyl group.

Reactive substituents which react while condensing are, for example, on the one hand the amino and hydroxyl groups and on the other, for example, the earboxylic acid or sulphonic acid halide groups or mobile, nuclearly bound halogen. For example, 1-amino-4-bromoanthraquinone-2-sulphonic acid is condensed by methods known per se with an arylamine to form 1-amino-4-arylaminoanthraquinone-Z-sulphonic acid, choosing as arylamine an aromatic amine which already contains at least one benzene monocarboxylic acid amidomethyl group which is possibly further substituted in the benzene nucleus.

The possibility of introducing further sulphonic acid groups into the reaction products after the amidomethylation has already been referred to above. It is also possible, however, to introduce other substituents into the amidomethylation products subsequently; in particular they can be subsequently brominated.

The anthraquinone dyestuffs produced according to the invention, in particular those which contain not more than two acid water solubilising groups, are suitable for the dyeing and printing of fibres containing polypeptide groups such as, e.g. leather, silk, superpolyamide and superpolyurethane fibres and, in particular, wool. From an acid aqueous bath, the dyestuffs draw very evenly onto these materials. Even in weakly acid to neutral solution, many of them have a high affinity to the nitrogenous fibres mentioned and thus have very good drawing power. The dyeings so obtained, in particular the wool dyeings, are very level and wet fast, e.g., they have good fastness to washing and milling, also in an alkaline medium. In addition, the dyeings often have very good fastness to light.

Particularly valuable, principally in view of their shades and very good fastness properties, are those dyestuffs according to the invention which correspond to the general formula CHz-NH-O C (SOsHh A represents a member selected from the group consisting of a-aminoanthraquinonyl-a'-imino,anthraquinonyla,a-di-imino, a,a-diaminoanthraquinonyl-;8,B-dioxy and a-aminoanthraquinonyl-oU-imino-fi-oxy radicals, the radical YD'I wherein Of these dyestuffs, those are preferred which are derived from 1,4-diaminoanthraquinone.

Further details can be seen from the following examples. These serve to illustrate the invention without limiting it in any way. Where not otherwise stated, parts are given therein as parts by weight and their relationship to parts by volume is as that of grammes to cubic centimetres. The temperatures are in degrees centigrade.

Example 1 12.9 parts of the sodium salt of the dyestuff of the formula obtained by condensation of 1 mol of l-amino-4-bromoanthraquinone-2-sulphonic acid with 1 mol of 1-amino-2- methylbenzene, are dissolved in parts of 96% sulphuric acid at 10 15". 7 parts of N-methylol-2,4-dichlorobenzamide (obtained by reacting 2,4-dichlorobenzamide with formaldehyde in alkaline, aqueous/ alcoholic solution; M.P. 122) are added and the mixture is stirred for 24 hours at this temperature. The mixture is poured onto -ice and the precipitated dyestufi isfiltered' 011'. It is pasted in Water, the pH is carefully adjusted to 7 with caustic soda lye and the dyestutf is precipitated in the form of its sodium salt by the addition of sodium chloride. From a weakly acid to neutral bath, this dyestuif produces very fast blue dyeings on Wool.

If, in the same process instead of the methylol compound mentioned, 5.85 parts of N-methylol-Z-chlorobenzamide (obtained by reacting Z-chlorobenzamide with formaldehyde in alkaline, aqueous solution; M.P. 108) are used or if 5.85 parts of N-methylol-4-chlorobenzamide (obtained by reacting 4-chloro benzamide with formaldehyde in aqueous, alkaline solution; M.P. 125 are used or if 6.5 parts of N-methylol-4-tert. butylbenzamide are used, then dyestulfs havingsimilar properties are obtained.

Example 2 12.9 parts of the sodium salt of the dyestulf of the formula 0 NHi H I SOaH are dissolved in 130 parts of 96% sulphuric acid at 15. 6.2 parts of N-methylol-4-nitrobenzamide (obtained by reacting 4-nitrobenzamide with formaldehyde in alkaline, aqueous/alcoholic solution;'M.P. 126) are added to this solution whereupon the mixture is stirred for 24 hours at 1=0-l5. The mixture is poured onto ice and the dyestufi is isolated in the form of the sodium salt in the usual way. The wool dyeings obtained with this dyestuff have good fastness properties.

If, in otherwise the same procedure, an isomeric methylol compound is used, namely 6.2 parts of N1 methylol-Z-nitrobenzamide (obtained by reacting Z-nitrobenzamide with formaldehyde in alkaline, aqueous/alcoholic solution), then a dyestulf having similar properties is obtained. 7

Example 3 13.75 parts of the sodium salt of the dyestuff of the formula fl) NHQ SOaH obtained by condensing 1 mol of l-amino-4-bromoanthraquinone-Z-sulphonic acid with 1 mol of l-amino-2,4,6- trirnethylbenzene, are dissolved at 10l5 in 140 parts of 96% sulphuric acid, andthen 7 parts of N-methylol-2,4- dichlorobenzamide are added. The mixture is stirred for 24 hours at 10'-15, then poured onto ice and the dyestuif is isolated in the form of the sodium salt in the usual way. The blue wool dyeings obtained with this dyestuff from a weakly acid to neutral bath have very good wet fastness properties.

If, in the condensation under otherwise the same conditions, 7 parts of N-methylol-dichlorobenzamide (obtained from a technical dichlorobenzoic acid which is produced by chlori'nating and oxidising toluene and, apart from trichlorobenzoic acid consists chiefly of 2,4- or -2,6- dichlorobenzoic acid) or of 5.85 parts of N-methylol-Z- 13.3 parts of the sodium salt of the dyestulf of the formula obtained by condensation of 1 mol of 1-amino-4-bromoanthraquinone-Z-sulphonic acid with 1 mol of l-amino- 2.,4-dimethylbenzene, are dissolved at 1015 in parts of 96% sulphuric acid. 7 parts of N-methylol-2,4-dichlorobenzarnide are added to the mixture whereupon it is stirred for 24 hours at the same temperature. The solution is poured onto ice and the dyestulf is isolated as described in Example 1. Blue Wool dyeings are obtained with the new dyestufi from a weakly acid bath, which dyeings have good wet fastness properties.

If, under otherwise the same conditions, instead of the dyestuif of the above formula, 12.9 parts of the sodium salt of the condensation product of 1 mol of 1-amino-4- bromoanthraquinone-2-sulphonic acid and 1 mol of 1- amino-4-methylbenzene is used, then a dyestutf is obtained which also dyes Wool fast blue shades.

A dyestutf having similar properties to that first described above is also obtained by stirring for 6 hours at 75-80" a mixture of 40.4 parts of the sodium salt of 1- amino-4-bromoanthraquinone-Z-sulphonic acid, 500 parts of 40% methanol, 20 parts of sodium bicarbonate, 0.8 part of cuprous chloride and 65 parts of the amine obtained by condensation of 1 mol of 1-amino-2,44limethylbenzene with 1 mol of N-methylol-2,4-dichlorobenzamide in 96% sulphuric acid. The methanol is then distilled off, the dyestufr" which precipitates in the form of the sodium salt is filtered off and is washed with 1% sodium chloride solution. When dry, the dyestuff is a blue powder which dissolves in Water with a blue colour.

Example 5 14.22 parts of the condensation product of 1 mol of quinizarine or leucoquinizarine and 2 mols of l-amino- 2,4,6-trimethylbenzene, corresponding to the formula are dissolved at 10-15 in parts of sulphuric acid monohydrate and 14 parts of N-methylol-2,4-dichlorobenzamide are added. The mixture is stirred for 24 hours at 10-15 and then poured onto ice. The precipitate obtained is filtered off, washed neutral and dried. This blue condensation product dissolves in organic solvents with a blue colour and on sulphonating in 10% oleum at 15-18 for 24 hours, it produces a dyestulf which is mainly disulphonated. It dyes wool in very wet fast blue shades from a weakly acid bath.

If, instead of the chlorinated methylol compound, 15.2 parts of N-methylol-o-brornobenzarnide or 20.5 parts of N-methylol-2,4-dibromobenzamide or 9.5 parts of N- methylol-benzamide or 11.3 parts of N-methylol-2,4- or -3,4-dimethyl benzamide are used under otherwise the same conditions, then dyestufis having similar properties are obtained.

N-methylol-o-bromobenzamide, N methylol 2,4 dibromobenzamide and N-methylol-2,4- or -3,4-dimethyl benzamide are obtained by reacting the corresponding benzamides with formaldehyde in alkaline, aqueous/ alcoholic solution.

Example 6 16.25 parts of the condensation product of 1 mol of 6,7-dichloroqninizarine and 2 mols of 1-amino-2,4,6-trimethylbenzene which corresponds to the formula NH -OH: 01- CH:

C1 CIF NH OH;

I CHg are dissolved at -l5 in 170 parts of sulphuric acid monohydrate and 14 parts of N-methylol-2,4-dichlorobenzamide are added. The solution is stirred for 24 hours at 10-15 and then poured onto ice. The condensation product which precipitates is then filtered off, washed neutral and dried. On sulphonating in 10% oleum for 24 hours at 18-20 a dyestuif is obtained which dyes wool from a weakly acid to neutral bath a greenish blue shade. The dyeings have good wet and light fastness properties.

If, under otherwise the same conditions, instead of the dyestuff mentioned above, 15.25 parts of the condensation product of 1 mol of 6-chloroquinizarine and 2 mols of 1-amino-2,4,6-trimethylbenzene or 16.6 parts of the condensation product of 1 mol of fi-bromoquinizarine and 2 mols of 1-amino-2,4,6-trimethylbenzene are used, then dyestuffs which also dye wool a very fast blue shade are obtained.

If, in these condensations, under otherwise the same conditions, 11.7 parts of N-methylol-2-chlorobenzamide are used instead of N-methylol dichlorobenzamide, then dyestuffs having similar properties are obtained.

Example 7 18.1 parts of the dye base of the formula are dissolved at 1015 in 180 parts of sulphuric acid monohydrate and 11.7 parts of N-methylol-Z-chlorobenzamide are added. The mixture is stirred for 24 hours at 1015, then poured onto ice, the product which precipitates is filtered ofi, washed neutral and dried.

After sulphonating for 2 hours at 10-12" in 33% oleum, a dyestuft which is mostly disulphonated is obtained from the condensation product. It dyes wool a reddish blue shade from a weakly acid to neutral bath and the dyeings have very good wet fastness properties.

If, instead of N-methylol-2-chlorobenzamide, 14 parts of N-methylol-2,4dichlorobenzarnide or 14 parts of N- methylol dichlorobenzamide (obtained from a technical dichlorobenzoic acid by chlorinating and oxidising toluene, consisting apart from trichlorobenzoic acid mainly of 2,4- or 2,6-dichlorobenzoic acid) are used under otherwise the same procedure, then a dyestufi having similar properties is obtained.

Example 8 15.4 parts of the dye base of the formula are dissolved in 160 parts of sulphuric acid monohydrate at 10-15 and 14 parts of N-methylol-2,4-dichlorobenzamide are added. The mixture is stirred for 24 hours at 1015, then poured onto ice and the product which precipitates is filtered off, washed neutral and dried. On sulphonating the condensation product in 33% oleum for 2 hours at 10-12", a dyestuff is obtained which produces wet fast, reddish blue dyeings on wool from a weakly acid bath.

If, under otherwise the same conditions, 11.7 parts of N-methylol-2-chlorobenzamide are used instead of N- methyl-2,4-dichlorobenzamide, then a dyestufi which has similar properties is obtained.

Example 9 9.96 parts of the condensation product of 1 mol of quinizarine and 2 mols of 1,2,3,4-tetrahydro-2-naphthylamine, which corresponds to the formula are mixed with 9.2 parts of N-rnethylol-2,4-dichlorobenzamide and the mixture is added at 05 to parts of 96% sulphuric acid. The mixture is stirred for 24 hours at 5, then poured onto ice and the precipitated product is filtered off, washed neutral and dried. After sulphonating the condensation product in 10% oleum for 24 hours at 1518, a dyestufi is obtained which dyes wool blue from a weakly acid bath. The dyeings are wet fast.

If, under otherwise the same conditions, the number of parts of dye bases given in the following Table 1 are used instead of the 9.96 parts of the above condensation product, then dyestuffs which have similar good properties are obtained.

TABLE 1 No. Parts Dye base Shade on wool H if F Brm II I O NH 2 11.32 Grecnish blue.

O NH H II I O NH H El) NH I H 1 HO 0 NH 7 4 10. 60 Blue green.

H HO (H) IIIH l H y 1 HO O NH Example 10 12.54 parts of the condensation product'of 1 mol of quinizarine and 2 mols of 1-arnino-4-methylbenzene 6 which corresponds to the formula are dissolved at 1015 in 130 parts of 96% sulphuric acid and 14 parts of N-methylol-2,4-dichlorobenzamide are added. The mixture is stirred for 24 hours at 1015 5 whereupon it is poured onto ice and the precipitated con- 75 good properties.

TABLE 2 N0. Parts Dye base Shade on wool i F'O 1- 14.9 Green.

H I O NH -CH3 t a g O NH- CHa t a 13.00 [Q3 Do.

HO O NH CH3 HO 4 e-O- 4 13. 5 m Yellowlsh green.

HO NH CHa Example 11 Example 12 12.75 parts of the dye base of the formula 12.54 parts of the dye base of the formula 0 NH ll I 45 +0 ll O NH: 50 mixed with 14 parts of N-methylol-Z,4 dichlorobenzamide H l are added at 05 to 140 parts of 90% sulphuric acid NH- CH; whereupon the mixture is stirred for 24 hours at The solution is poured onto ice and the precipitate of the prodare dissolved at -15 in 130 parts of 96% sulphuric acid and 11.25 parts of N-methylol-2,4-dimethylbenzarnide are added. The mixture is stirred for 24 hours at 10- 15 whereupon it is poured onto ice and the precipitated condensation product is filtered off, washed neutral and dried. On sulphonating the reaction product in 10% 01eum for 24 hours at 10-l5, a dyestuff is obtained which dyes wool a wet fast green shade from a weakly acid bath.

If, under otherwise the same conditions, instead of N- methylol-2,4-dimethylbenzamide, 11.25 parts of N-methy-lol-3,4-dimethylbenzamide or 12.4 parts of N-methylol- 4- or -2-nitrobenzarnide or 14.3 parts of N-rnethylol-diphenyl carboxylic acid amide (obtained by reacting diphenyl carboxylic acid amide with formaldehyde in an alkaline aqueous/ alcoholic solution), or if 12.66 parts of N-rnethylol napthalene-Z-carboxylic acid amide (obtained by reacting napthalene-Z-carboxylic acid amide with formaldehyde in an alkaline, aqueous/ alcoholic solution) are used, then dyestuffs having similar good properties are obtained.

not is filtered 01f, washed neutral and dried. On sulphonating the condensation product in 10% oleurn for 24 hours at 13-15", a dyestulf which is mostly disul-phonated is obtained. It produces wet fast, red-violet wool dyeings from a weakly acid bath.

If, under otherwise the same conditions, 16.1 parts of the dye base of the formula NHa n 000411. 0 NH:

O NH;

13 are used instead of the dye base mentioned above, then dyestuffs are obtained which also dye wool a fast red violet shade from a Weakly acid bath.

Dyestuffs having similar properties are also obtained if, instead of N-methylol-2,4-dichlorobenzamide, 13 parts of Namethylol-4-tert. butylbenzamide or 14.3 parts of N- methylol-diphenyl carboxylic acid amide or 12.7 parts of N-methylol-napthalene-Z-ca-rboxylic acid amide are used.

8.26 parts of the unsulphonated condensation product first mentioned above are dissolved at 810 in 100 parts of 96% sulphuric acid whereupon 1.8 parts of bromine are added and the whole is stirred at the same temperature for 16 hours.

The mixture is poured onto ice and the precipitate of the product is filtered off, washed neutral and dried. On sulphonating the bromine-containing condensation product in 20% oleum at 15-18 for 8 hours, a dyestuff is obtained which also dyes wool a red violet shade from a Weakly acid bath. Compared with the dyestuff not containing bromine, it has a better drawing power from a neutral medium.

Dyestuffs having similar properties are also obtained it 15.2 parts of N-methylol-o-bromo'benzamide or 20.5 parts of N-methylol-2,4-dibromobenzamide are used instead of N-methylol-2,4-dichlorobenzamide.

Example 13 13.50 parts of the dye base of the formula NH: ii I mixed with 14 parts of N-methylol-2,4-dichlorobenzamide are added at 02 to 150 parts of 90% sulphuric acid whereupon the mixture is stirred for 24 hours at 2. The solution is poured onto ice and the precipitate of the product is filtered off, washed neutral and dried. On sulphonating the condensation product with oleum for 30 minutes at 45", 1a dyestutf is obtained which dyes wool la blue violet shade from a weakly acid 'bath. The dyeings are wet fast.

If, with otherwise the same procedure, 13.1 parts of the dye base of the formula i) NHg CH are used instead of the dye base mentioned above, then a dyestuff which dyes wool fast in a reddish blue shade is obtained.

Dyestuffs having similar properties are also obtained if, instead of N-methylol-2,4-dichlorobenzamide, 11.7 parts of N-methylol-Z-chlorobenzamide are used.

Example 14 15.60 parts of the dye base of the formula (II) JTYI'IZ O O C.H..

(lam b NHOCH: la.

mixed with 7 parts of N-methylol-2,4-dichlorobenzamide are added at O -5 to 170 parts of sulphuric acid. The mixture is stirred for 24 hours at 5 whereupon the solution is poured onto ice, the precipitated product is filitered off, washed neutral and dried. On sulphonating the condensation product in 10% oleum for 30 minutes at 45, a dyestutf is obtained which dyes wool a blue violet shade from a weakly acid bath. The dyeing is wet fast.

If, under otherwise the same conditions, 5.8 parts of N- methylol-2-chlorobenzamide are used, then a dyestulf having similar properties is obtained.

Example 15 10 g. of woolen flannel are immersed at 40 in a dyebath prepared from 500 ml. of water, 0.5 g. of sodium sulfate, 0.4 g. of acetic acid and 0.2 g. of the dyestuif of Example 7. The temperature of the bath is gradually raised within 30 minutes to the boiling point and the bath then kept at the boil for one hour. The dyed woolen fabric is Withdrawn from the bath, rinsed with Water, and dried at room temperature. There is obtained a very level, brilliant reddish-blue dyeing.

I claim:

1. A dyestuff of the formula wherein A represents 1-amino-2-sulfo-anthraquinonyl-4-imino,

Y represents a member selected from the group consisting of hydrogen and lower alkyl,

Y represents a member selected from the group consisting of hydrogen and lower alkyl,

Z represents a member selected from the group consisting of hydrogen, chlorine and bromine in at least one of the positions ortho and para to the -CO p q is an integer ranging from 1 to 2.

2. A dyestuff of the formula II I 0 MG... 0.

Had (BHPNH-QUGCI characterized by wet fastness.

(References on following page) 15 16 References Cited by the Examiner FOREIGN PATENTS UNITED STATES PATENTS 1,222,194 1/ 1960 France.

1,927,125 9/1933 *Kalischer 260372 2,245,780 6/1941 Heinrich 260-372 5 RICHARD JACKSPN, 'f

H. C. WEGNER, Asszstant Exammer.

LORRAINE A. WEINBERGER, Primary Examiner. 

1. A DYESTUFF OF THE FORMULA 